Solid, polymer, surface properties

For polymer surface properties controlled by the chemical composition, thermodynamic (equihbrium), non-equihbrium, and technical terms and definitions play an important role. These are not always used in a consistent way, hence a short recapitulation seems appropriate. The thermodynamic work of adhesion (Wa) is defined as the reversible work (the free energy change) required to separate two phases with unit area of contact, from contact to infinity. The corresponding work of adhesion (and cohesion for similar bodies) can be easily expressed with surface tension values. In general, for surfaces of two intimately contacting solids ( l and 2 , respectively) each with a unit area, are separated in a medium ( 3 ), a work VT132 is required which can be expressed as ... 

Surface Protection. The surface properties of fluorosihcones have been studied over a number of years. The CF group has the lowest known intermolecular force of polymer substituents. A study (6) of liquid and solid forms of fluorosihcones has included a comparison to fluorocarbon polymers. The low surface tensions for poly(3,3,3-trifluoropropyl)methylsiloxane and poly(3,3,4,4,5,5,6,6,6-nonafluorohexyl)methylsiloxane both resemble some of the lowest tensions for fluorocarbon polymers, eg, polytetrafluoroethylene. 

N.S. Cohen et al, A1AA J 12 (2), 212-18 ( qia QQt 135471 (1974V The effects of inert polymer binder properties on composite solid proplnt burning rate are described. Surface pyrolysis data for many polymers over a wide range of conditions are used to derive kinetics constants from Arrhenius plots and heat of... 

Dole, M. Calorimetric Studies of States and Transitions in Solid High Polymers. Vol. 2, pp. 221-274. Donnet, J. B., Vidal, A. Carbon Black-Surface Properties and Interactions with Elastomers. Vol. 76, pp. 103-128. 

A surface is that part of an object which is in direct contact with its environment and hence, is most affected by it. The surface properties of solid organic polymers have a strong impact on many, if not most, of their apphcations. The properties and structure of these surfaces are, therefore, of utmost importance. The chemical stmcture and thermodynamic state of polymer surfaces are important factors that determine many of their practical characteristics. Examples of properties affected by polymer surface stmcture include adhesion, wettability, friction, coatability, permeability, dyeabil-ity, gloss, corrosion, surface electrostatic charging, cellular recognition, and biocompatibility. Interfacial characteristics of polymer systems control the domain size and the stability of polymer-polymer dispersions, adhesive strength of laminates and composites, cohesive strength of polymer blends, mechanical properties of adhesive joints, etc. 

In this brief review we illustrated on selected examples how combinatorial computational chemistry based on first principles quantum theory has made tremendous impact on the development of a variety of new materials including catalysts, semiconductors, ceramics, polymers, functional materials, etc. Since the advent of modem computing resources, first principles calculations were employed to clarify the properties of homogeneous catalysts, bulk solids and surfaces, molecular, cluster or periodic models of active sites. Via dynamic mutual interplay between theory and advanced applications both areas profit and develop towards industrial innovations. Thus combinatorial chemistry and modem technology are inevitably intercoimected in the new era opened by entering 21 century and new millennium. 

We have already referred to the Mo/Ru/S Chevrel phases and related catalysts which have long been under investigation for their oxygen reduction properties. Reeve et al. [19] evaluated the methanol tolerance, along with oxygen reduction activity, of a range of transition metal sulfide electrocatalysts, in a liquid-feed solid-polymer-electrolyte DMFC. The catalysts were prepared in high surface area by direct synthesis onto various surface-functionalized carbon blacks. The intrinsic... 

If solid polymer objects are fluorinated or polymer particles much larger than 100 mesh are used, only surface conversion to fluorocarbon results. Penetration of fluorine and conversion of the hydrocarbon to fluorocarbon to depths of at least 0.1 mm is a result routinely obtained and this assures nearly complete conversion of finely powdered polymers. These fluorocarbon coatings appear to have a number of potentially useful applications ranging from increasing the thermal stability of the surface and increasing the resistance of polymer surfaces to solvents and corrosive chemicals, to improving friction and wear properties of polymer surfaces. It is also possible to fluorinate polymers and polymer surfaces partially to produce a number of unusual surface effects. The fluorination process can be used for the fluorination of natural rubber and other elastomeric surfaces to improve frictional characteristics and increase resistance to chemical attack. 

---